US2763636A - Method of controlling molecular weight of polyacrylonitrile produced in aqueous salt solutions - Google Patents
Method of controlling molecular weight of polyacrylonitrile produced in aqueous salt solutions Download PDFInfo
- Publication number
- US2763636A US2763636A US306310A US30631052A US2763636A US 2763636 A US2763636 A US 2763636A US 306310 A US306310 A US 306310A US 30631052 A US30631052 A US 30631052A US 2763636 A US2763636 A US 2763636A
- Authority
- US
- United States
- Prior art keywords
- polymer
- molecular weight
- solution
- weight
- solutions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/42—Nitriles
- C08F20/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
Definitions
- This invention relates to a method of controlling the molecular weight of the polymer obtained when acrylonitrile is polymerized in an aqueous saline medium which dissolves both the monomer and the polymer.
- acrylonitrile may be polymerized in concentrated aqueous solutions of certain salts to form solutions of the polymer, and that the polymer solutions may be used to spin fibers.
- the salt solutions which may be used include the zinc halides, stannic halides, and the calcium or sodium thiocyanates, as disclosed in the art.
- some solutions of mixed salts can be used in which one salt is capable at higher concentrations of dissolving the polymer and the other salt is incapable alone of dissolving the polymer at any concentration of that salt in water.
- Such useful mixtures include zinc chloride and lesser amounts of calcium chloride, zinc chloride and lesser amounts of magnesium chloride, zinc bromide and lesser amounts of lithium chloride, sodium thiocyanate and lesser amounts of potassium thiocyanate, as described by the present inventor and others in copending application Serial No. 228,752, filed May 28, 1951, now U. S. Patent No. 2,648,647.
- the salt concentration in the useful solutions, as shown in said patent, must be at least 55 per cent but need not exceed 65 per cent, by weight.
- the foregoing and related objects are attained through control or adjustment of the concentration of copper ions in the saline polymeriice 2 zation medium. More specifically, it is found that, to obtain polymers with molecular weights controlled in the range from 12,000 to 125,000, the saline medium should contain correspondingly from 1.0 to 0.02 part of copper ions per million partsby weight of the salt solution. Similarly, the most generally useful polymers, having molecular weights in the range from about 20,000 to about 70,000 are obtained consistently when there is present in the saline medium from about 0.5 to about 0.03 part of copper ions per million parts of the salt solution.
- test ion was added to the zinc chloride solution in an amount representing 5 parts of that ion by weight per million parts of the solution.
- One part by volume of acrylonitrile monomer was dissolved in six volumes of the so-modified salt solution, and 1 per cent by weight of potassium persulfate, based on the weight of monomer, was used in each case as the catalyst.
- Polymerization was effected at 50 C.
- each of those solutions was of a practical spinning viscosity, except when copper was present, and the polymer recovered from each of the solutions had a molecular weight of the same order of magnitude as that made in the original zinc chloride, except that made in the solution containing 5 parts per million of the cupric ion as an impurity.
- Example 1 Acrylonitrile was polymerized at 50 C. in each of several 60 per cent solutions of zinc chloride in water and in the presence of 0.15 per cent by weight of hydrogen peroxide based on the weight of monomer.
- the solutions contained the indicated concentrations of cupric ion.
- Example 2 The procedure and conditions of Example 1 were followed except that the polymerization medium was a solution in water of 45 per cent zinc chloride and per cent calcium chloride.
- Example 3 Acrylonitrile was polymerized at 50 C. in each of several solutions in water of 45 per cent zinc chloride and 15 per cent magnesium chloride, using 1 per cent of potassium persulfate as catalyst, based on the weight of monomer. The eifect of variation of copper ion concentration was observed as before.
- the invention is not limited in its applicability to the particular salt solutions identified in the examples but is of equal value when using any salt or mixture of salts whose aqueous solution is a solvent for both monomeric and polymeric acrylonitrile.
- aqueous salt solution contains zinc chloride as the principal solute, together with a lesser amount of calcium chloride.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE520071D BE520071A (es) | 1952-08-25 | ||
NL80986D NL80986C (es) | 1952-08-25 | ||
US306310A US2763636A (en) | 1952-08-25 | 1952-08-25 | Method of controlling molecular weight of polyacrylonitrile produced in aqueous salt solutions |
DED15085A DE1010276B (de) | 1952-08-25 | 1953-05-18 | Verfahren zur Polymerisation von Acrylnitril |
FR1082731D FR1082731A (fr) | 1952-08-25 | 1953-05-18 | Perfectionnements à un procédé de polymérisation de l'acrylonitrile |
CH317133D CH317133A (de) | 1952-08-25 | 1953-05-19 | Verfahren zum Polymerisieren von Acrylnitril |
GB15256/53A GB725751A (en) | 1952-08-25 | 1953-06-01 | Improvements in or relating to a process of polymerising acrylonitrile |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US306310A US2763636A (en) | 1952-08-25 | 1952-08-25 | Method of controlling molecular weight of polyacrylonitrile produced in aqueous salt solutions |
Publications (1)
Publication Number | Publication Date |
---|---|
US2763636A true US2763636A (en) | 1956-09-18 |
Family
ID=23184733
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US306310A Expired - Lifetime US2763636A (en) | 1952-08-25 | 1952-08-25 | Method of controlling molecular weight of polyacrylonitrile produced in aqueous salt solutions |
Country Status (7)
Country | Link |
---|---|
US (1) | US2763636A (es) |
BE (1) | BE520071A (es) |
CH (1) | CH317133A (es) |
DE (1) | DE1010276B (es) |
FR (1) | FR1082731A (es) |
GB (1) | GB725751A (es) |
NL (1) | NL80986C (es) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2837492A (en) * | 1954-02-10 | 1958-06-03 | Dow Chemical Co | Process of making colorless aqueous saline solutions of polyacrylonitrile |
US3044975A (en) * | 1957-01-17 | 1962-07-17 | Bayer Ag | Process for the production of spinning solutions of polyacrylonitrile |
US3112295A (en) * | 1959-03-05 | 1963-11-26 | Du Pont | Emulsion polymerization of water-soluble with water-insoluble monomers |
US3282878A (en) * | 1965-07-26 | 1966-11-01 | Dow Chemical Co | High acrylonitrile polymer solutions containing 2, 4, 6-trichlorophenol |
US3282877A (en) * | 1965-07-26 | 1966-11-01 | Dow Chemical Co | High acrylonitrile polymer solutions containing brominated salicylanilides |
US3284395A (en) * | 1965-07-26 | 1966-11-08 | Dow Chemical Co | High acrylonitrile polymer solutions containing a mixture of monochlorinated orthophenylphenols |
US3287307A (en) * | 1965-03-29 | 1966-11-22 | Toho Rayon Kk | Method for preparation of the solution of acrylonitrile polymer |
US4123406A (en) * | 1970-03-26 | 1978-10-31 | Ceskoslovenska Akademie Ved | Method of preparing shaped articles from cross-linked hydrogels |
US4172823A (en) * | 1970-03-26 | 1979-10-30 | Ceskoslovenska Akademie Ved | Method of preparing cross-linked hydrogels |
US4228056A (en) * | 1969-06-13 | 1980-10-14 | Ceskoslovenska Akademie Ved | Shaped articles from insoluble hydrogels and method of manufacturing same |
US4725364A (en) * | 1982-04-05 | 1988-02-16 | Basf Corporation | Laminar flow filtration process |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1191965B (de) * | 1958-11-24 | 1965-04-29 | Artur Stoy Dipl Ing | Verfahren zur Herstellung von spinnfaehigen Loesungen von Polymeren bzw. Copolymeren des Acrylnitrils in konzentrierten waessrigen Salzloesungen |
DE1211162B (de) * | 1959-10-31 | 1966-02-24 | Hans J Zimmer Verfahrenstechni | Verfahren zur Entfernung der in reinem, wasserfreiem Acrylsaeurenitril vorhandenen Spuren Kupfer |
GB987754A (en) * | 1960-07-09 | 1965-03-31 | Toho Rayon Kk | Method for the preparation of solutions of acrylonitrile polymers |
AT261212B (de) * | 1964-03-23 | 1968-04-10 | Ministerul Ind Petrolului | Verfahren zur Gewinnung von Halbleitern auf Basis von Polyacrylnitril |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2356767A (en) * | 1940-04-26 | 1944-08-29 | American Cyanamid Co | Process of producing polymeric materials |
US2379431A (en) * | 1941-06-27 | 1945-07-03 | Goodrich Co B F | Polymerization of butadienes |
GB599472A (en) * | 1945-09-18 | 1948-03-12 | Michael Carr Ashworth | Improved method of polymerisation |
US2477784A (en) * | 1944-03-06 | 1949-08-02 | Dow Chemical Co | Polymerization of vinyl aromatic compounds |
US2486943A (en) * | 1946-08-31 | 1949-11-01 | Montclair Res Corp | Polymerization process in aqueous thiocyanate solutions |
US2601293A (en) * | 1950-04-01 | 1952-06-24 | Du Pont | Polymerization initiation systems comprising a hydrazone, a peroxy compound, and cupric ion |
US2648647A (en) * | 1951-05-28 | 1953-08-11 | Dow Chemical Co | Polymerizing acrylonitrile in aqueous mixed salts |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH251650A (de) * | 1945-02-09 | 1947-11-15 | Du Pont | Verfahren zur Polymerisation von Monoäthylenverbindungen. |
-
0
- NL NL80986D patent/NL80986C/xx active
- BE BE520071D patent/BE520071A/xx unknown
-
1952
- 1952-08-25 US US306310A patent/US2763636A/en not_active Expired - Lifetime
-
1953
- 1953-05-18 DE DED15085A patent/DE1010276B/de active Pending
- 1953-05-18 FR FR1082731D patent/FR1082731A/fr not_active Expired
- 1953-05-19 CH CH317133D patent/CH317133A/de unknown
- 1953-06-01 GB GB15256/53A patent/GB725751A/en not_active Expired
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2356767A (en) * | 1940-04-26 | 1944-08-29 | American Cyanamid Co | Process of producing polymeric materials |
US2379431A (en) * | 1941-06-27 | 1945-07-03 | Goodrich Co B F | Polymerization of butadienes |
US2477784A (en) * | 1944-03-06 | 1949-08-02 | Dow Chemical Co | Polymerization of vinyl aromatic compounds |
GB599472A (en) * | 1945-09-18 | 1948-03-12 | Michael Carr Ashworth | Improved method of polymerisation |
US2486943A (en) * | 1946-08-31 | 1949-11-01 | Montclair Res Corp | Polymerization process in aqueous thiocyanate solutions |
US2601293A (en) * | 1950-04-01 | 1952-06-24 | Du Pont | Polymerization initiation systems comprising a hydrazone, a peroxy compound, and cupric ion |
US2648647A (en) * | 1951-05-28 | 1953-08-11 | Dow Chemical Co | Polymerizing acrylonitrile in aqueous mixed salts |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2837492A (en) * | 1954-02-10 | 1958-06-03 | Dow Chemical Co | Process of making colorless aqueous saline solutions of polyacrylonitrile |
US3044975A (en) * | 1957-01-17 | 1962-07-17 | Bayer Ag | Process for the production of spinning solutions of polyacrylonitrile |
US3112295A (en) * | 1959-03-05 | 1963-11-26 | Du Pont | Emulsion polymerization of water-soluble with water-insoluble monomers |
US3287307A (en) * | 1965-03-29 | 1966-11-22 | Toho Rayon Kk | Method for preparation of the solution of acrylonitrile polymer |
US3282878A (en) * | 1965-07-26 | 1966-11-01 | Dow Chemical Co | High acrylonitrile polymer solutions containing 2, 4, 6-trichlorophenol |
US3282877A (en) * | 1965-07-26 | 1966-11-01 | Dow Chemical Co | High acrylonitrile polymer solutions containing brominated salicylanilides |
US3284395A (en) * | 1965-07-26 | 1966-11-08 | Dow Chemical Co | High acrylonitrile polymer solutions containing a mixture of monochlorinated orthophenylphenols |
US4228056A (en) * | 1969-06-13 | 1980-10-14 | Ceskoslovenska Akademie Ved | Shaped articles from insoluble hydrogels and method of manufacturing same |
US4123406A (en) * | 1970-03-26 | 1978-10-31 | Ceskoslovenska Akademie Ved | Method of preparing shaped articles from cross-linked hydrogels |
US4172823A (en) * | 1970-03-26 | 1979-10-30 | Ceskoslovenska Akademie Ved | Method of preparing cross-linked hydrogels |
US4725364A (en) * | 1982-04-05 | 1988-02-16 | Basf Corporation | Laminar flow filtration process |
Also Published As
Publication number | Publication date |
---|---|
BE520071A (es) | |
FR1082731A (fr) | 1954-12-31 |
GB725751A (en) | 1955-03-09 |
NL80986C (es) | |
CH317133A (de) | 1956-11-15 |
DE1010276B (de) | 1957-06-13 |
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